Process for breaking petroleum emulsions employing certain amine-modified thermoplastic phenol-aldehyde resins



United States PatentO Melvin De Groote, University City, Mo., assignor to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. 7 Application September 23, 1953 Serial No. 381,980

10 Claims. (Cl. 252344) -Attention is directed to my co-pending applications,

Serial Numbers 288,742, through 288,746, inclusive, filed May 19, 1952, all now abandoned. The first of said co-pending applications relates to synthetic condensation products obtained by condensing certain phenol-aldehyde resins, therein described in detail, with certain basic nonlhydroxylated secondary monoamines, also therein described in detail, and formaldehyde.

The second application is similar to the first except that the monoamines employed as reactants are hydroxylated instead of being nonhydroxylated. The third application is similar to the first one insofar that nonhydroxylated polyamines are employed as reactants. The fourth application is concerned with hydroxylated polyamines as reactants and the last application is concerned with amines having a cyclic amidine group in the reactant regardless of whether it is hydroxylated or not.

The present application is differentiated from the aforementioned five applications in that the aldehyde used, in stead of being formaldehyde, is furfural. Stated another way, this invention is concerned with certain heat-stable oxyalkylation-susceptible resinous condensation products obtained by condensing certain phenol-aldehyde resins, hereinafter described in detail, with certain basic secondary amines, also hereinafter described in detail, and furfural.

For purpose of illustration it may be simpler to divert momentarily to the products described in the five aforementioned co-pending applications, Serial Nos. 288,742 through and including 288,746, inclusive, and for sake of simplicity to the first one, i. e., Serial No. 288,742, in which the amine reactant is a nonhydroxylated monoamine. For purpose of simplicity the invention described in said co-pending application, Serial No. 288,742, may be exemplified by an idealized formula, as follows:

although obviously other aldehydes are equally satisfactory. The amine residue in the above structure is de-v rived from a basic amine, and usually a strongly basic amine, and may be indicated thus:

R! in which R represents any appropriate hydrocarbon radical, such as an alkyl, alicyclic, arylalkyl radical, etc., free from hydroxyl radicals. The only limitation is that the radical should not be a negative radical, which considerably reducesthe basicity of the amine, such as an aryl radical or an acyl radical. Needless to say, the two occurrences of R may jointly represent a single divalent radical instead of two monovalent radicals. This is illustrated by morpholine and piperidine. The introduction of two such amino radicals into a comparatively small resin molecule, for instance, one having 3 to '6 phenolic nuclei as specified, alters the resultant product in a number of ways. In the first place, a basic nitrogen atom, of course, adds a hydrophile effect; in the second place, depending on the size of the radical R, there may be a counterbalancing hydrophobe effect or one in which the hydrophobe effect more than counterbalances the hydrophile eflect of the nitrogen atom. Finally, in such cases where R; contains one or more oxygen atoms, another etfect is introduced, particularly another hydrophile effect.

Such condensates, i. e., the condensates of Serial No. 288,742, and in fact the instant condensates, are obtained from phenol-aldehyde resins. It is well known that one can readily purchase on the open market, or prepare, fusible, organic solvent-soluble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula OH OH OH rel a] H H R R R In the above formula n represents a small whole number varying from 1 to 6, 7 or am more, up to probably 10 or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e.,. it varies from 1 to 4; R represents a hydrocarbon substituent, generally an alkyl radical having from 4 to 14 carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the 'divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

When in the preparation of certain phenol-aldehyde resin formaldehyde is replaced by furfural, precautions must be taken if one is attempting to obtain an organic solvent-soluble resin. The reason is that cross-linking is produced due to the unsaturation of .furfural in addition to its usual functionality as an aldehyde. This has been stated briefly as followsz-- i Other aldehydes than formaldehyde react readily with phenol, but these resinsare not commercially important except the reaction product of phenol with furfural. The condensation products are much darker in color, than the resins from formaldehyde. The resins are formed by the condensation of fu'rfural with phenol in alkaline solution. The condensates cure on heating to 350F. with evolution of heat. This polymerization'is believed to be of the vinyl type, involving the doublebonds in the furane ring HO OH Formaldehyde has been used along with furaldehyde in some instances. (See Synthetic Resins and Rubbers,

Powers, John Wiley & Sons, Inc., New York, 1943, page '78.)

Thus, it becomes apparent that the oversimplification which has, been previously presented in connection with must be rewritten in connection with furfural in the following manner: s

Revertmgagain to what is said in the five co-pending applications previously referred to, and particularly to Serial No. 288,742, reference is made to the text which describes other products of reaction which appear in the cogeneric mixture resultingfrom reaction between the resin, the secondary amine and formaldehyde. The reference is as follows:

In conducting reactions of thiskind one does not necessarily obtain a hundred percent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one mole of the aldehyde, or only one mole of the amine may combine with the resin molecule, or even to a very slight extent, if at all, 2 resin units may combine without any amine in the reaction product, as indicated in the following formulas:

When formaldehyde is replaced by furfural the three previous formulas become as follows:

Rl O

on l H El R R (B) OH 3 I- on a -l R R R R For reasons which are obvious from an examination of the literature concerned with the production of furane resins, and particularly resins in which furfural is involved no attempt has been made to show how any two I It is quite possible that in the presence of an alkaline catalyst as distinguished from an acid catalyst, polymerization does not go beyond adimer or a trimer. The types, of course, would be indicated as AA, BB, CC, DD, AB, AC, AD, BC, BD, etc. It is quite possible that at least some trimers are formed. .In any event, to the extent that there is present in a reaction mass involving formaldehyde certain products which may be considered byproducts it becomes obvious that these same types of resultants, i. e., the byproduct type of resultant, becomes part of a larger molecule when furfural is used. Thus it is quite possible that practically all theresultants of reaction involve the original amine and the original resin when furfural is used as the aldehyde, in this type of condensation. This is demonstratedby at least two facts, (a) substituting furfural for formaldehyde inany particular mixture one obtains a resin which is more apt to be solid, in fact, usually is solid rather than being a thick, viscous, tacky liquid, and shows a higher molecular weight by various procedures employed, although such methods are not necessarily completely satisfactory from an analytical standpoint; and (b) the products obtained from, furfural can be heated at temperatures higher than those herein described in the preparation of the products, and will not infrequently convert into an insoluble resin. At least in most instances the addition of more furfural with subsequent heating so converts them. Comparable condensates derived from vformaldehyde do not convert over in the presence of additional formaldehyde. Furthermore, the composition of thewinstant products are complicated by the fact that ,furfural as such might polymerize to a dimer prior to reaction and thus involve a different type of compound than in some mentioned previously. In any event, the condensates so obtained are diflerent in character and for some purposes particularly after oxyalkylation with ethylene oxide, propylene oxide, butylene oxide, glycide, or methylglycide and particularly elfective for the resolution of petroleum emulsions. Indeed, in many instances the oxyalkylation derivatives are distinctly more elfective than the comparable products derived from condensates in which formaldehyde is used.

For purpose of convenience what is said hereinafter will be divided into five parts:

Part 1 is concerned with phenol-aldehyde resins suitable for condensation;

Part 2 is concerned with suitable secondary amines which can be employed in conjunction with the resins in the condensation procedure;

Part 3 is concerned with the condensation procedure as such;

Part 4 is concerned with the uses of the condensates for the resolution of petroleum emulsions; and

Part 5 is concerned with uses for the condensates for purposes other than demulsification, and particularly for their use as initial raw materials which are subjected to oxyalkylation.

PART .1

This part is concerned with the preparation of phenolaldehyde resins of the kind described in detail in U. S. Patent No. 2,499,370, dated March 7, 1950, to De Groote and Keiser, with the following qualifications; said aforementioned patent is limited to resins obtained from difunctional phenols having 4 to 12 carbon atoms in the substituent hydrocarbon radical. For the present purpose the substituent may have as many as '18 carbon atoms, as in the case of resins prepared from tetradecyclphenol, substantially para-tetradecylphenol, commercially available. Similarly, resins can be prepared from hexadecylphenol or octadecylphenol. This feature will be referred to subsequently.

In addition to U. S. Patent No. 2,499,370, reference is made also to the following U. S. Patents: Nos. 2,499,- 365, 2,499,366, and 2,499,367, all dated March 7, 1950, to De Groote and Keiser. These patents, along with the other two previously mentioned patents, describe phenolic resins of the kind herein employed as initial materials.

"For practical purposes, the resins having 4 to 12 carbon atoms are most satisfactory, with the additional C carbon atoms also being very satisfactory. The increased cost of the C and C carbon atom phenol renders these raw materials of less importance, at least at the present time.

Patent 2,499,370 describes in detail methods of preparing resins useful as intermediates for preparing the products of the present application, and reference is made to that patent for such detailed description and to Examples 1a through 103a of that patent for examples of suitable resins.

As previously noted, the hydrocarbon substituent in the phenol may have as many as 18 carbon atoms, as illustrated by tetradecylphenol, hexadecylphenol and octadecylphenol, reference in each instance being to the difunctional phenol, such as the orthoor para-substituted phenol or a mixture of the same. Such resins are described also in issued patents, for instance, U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser, such as Example 7 la.

Reference has been made to an earlier formula which was in essence an over-simplification representing a phenolformaldehyde resin. Actually, some other aldehyde, such as acetaldehydre, propionaldehyde, or butyraldehyde, may be used. The resin unit can be' exempli R R n R in which R is the divalent radical obtained from the particular aldehyde employed to form the resin.

As previously stated, the preparation of resins of the kind herein employed as reactants is 'well known. See U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. Resins can be made using an acid catalyst or basic catalyst or a catalyst showing neither acid nor basic properties in the ordinary sense, or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst, such strong acid should be neutral- 5 units, or just 6 units, etc; It is usuallya mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins we found 'no reason for using other than those which are lowest in price and most readily available commercially; For purpose of convenience suitable resins are characterized in the following table:

TABLE I M01. wt Ex- R of resin ample R Position derived 'Il molecule number of R from- (based on n+2) 1a Phenyl. Para-. 3.5 992.5

211 Tertiary butyl do... 3.5 882.5 3a Sec0udarybutyl.. Orth0 3.5 882.5 OyclohexyL i 3. 5 1, 025. 5 Tertiary amyl 3. 5 959. 5 Mixed secondary 3.5 805.5

and tertiary amyl.

' 3.5 1,022. 5 any 3.5 1,330.5 Tertiary butyl. 3. 5 1,071. 5

Tertiary amyl j 3. ,6 '1, 148. 5 Nonyl 3. 5 1, 456. 5 Tertiary butyl 3. 5 1, 008. 5

Tertiary amyl 3. 5 1, 085.5 Nonyl 3.5 1,393.5 Tertiary butyL 4. 2 996. 6

Tertiary amyl 4.2 i 1, 083. 4 onyl d0. 4.2 1,430.6 Tertiary butyl d 4.8 1,094.4 Tertiary amy1 4. 8 1, 189. 6 ony 4.8 l, 570. 4 Tertiary amyL 1.5 604.0 1.5 646.0 1.5 653.0 1.5 688.0

6 cedure in practically every case is to havethe resin neutral. j v p I In preparing resins one does not get a single poly mer, i. e., one having just 3 units, or just 4 units, orjust PART 2 R in which R represents a monovalent' "alkyl, alicyclic, arylalkyl radical and may be heterocyclic in a few instances as in the case of piperidine and a secondary amine derived from furfurylamine by methylation or ethylation, or a similar procedure. 1 1

Another example of a heterocyclic amine is, of course, morpholine. V

The secondaryamines most readily available are, of

of the composition Y course, amines such as dimc hylamine, metlwleths im ine,

diethylamine, dipropylamine, ethylpropylamine, dibutyl Y amine, diamylarnine, dihexylarnine, dioctylamine, and 'di- -nonylaminea Oth'er amines include bis(1,3-dimethyl- 'butyDaminer There are of course, a variety of primary Y amines which can be reacted with an alkylating agent Y such as dimethyl sulfate, diethyl sulfate, and alkyl bro -mide, an ester of sulfonic acid-,.etc., to produce suitable 1 amines within the herein specified limitations. For ex. ample, one can methylate alphamethylbenzylamine, 01'' benzylamine itself, to produce a suitable reactant. Needless to say, one can use secondary amines such as dicyclohexylamine, dibutylamine or amines containing one cyclohexyl group and one alkyl group, or'one benzyl group and one alkyl group, such as ethylcyclohexylamine, ethyl benzylamine, etc. r Y Y i Y Other suitable compounds areexernplified by Y Y Other somewhatsimilar secondary amines are those IRO(C-H2)s as described in U. S. Patent No. 2,375,659 dated May 8, 1945, to Jones et a1. methyl, ethyl, propyl, amyl, octyl, etc.

Other amines can be obtained fromproducts which are sold in the open market, such as maybe obtained by alkylation of cyclohexylmetbylamine or the alkylation of similar primary amines, or, for that matter, amines of thev kind described in U. S. Patent No, 2,482,546,

dated September 20, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic In the above formula R may be 2.1 8 (c1130omomoiomouiocmom) HO-O=H4'/ eurocmcuaomcmcmonn Y TJONH HOG2 l or comparable compounds having two hydroxylated groups of dilferent lengths i i i (Holmrlouiocmomo ernon I HQCaH4 p "Other examples vof suitable amines include alphamethylbenzylamine and monoethanolamine; also amines I obtained by treating cyclohexylmethylamine with one Y mole of an oxyalkylatingagent as previously described;

beta ethylhexylbutanolamine, diglycerylam'ine, etc. An:

other typeof amine, which is of particular interest be-'- cause it includes a verydefinite hydrophile group he eludes sugar amines such as glucamine, galactamine and ,fructamine, such as: N-hydroxyethylglucamine, N -hy nucleus. Examples include the following: betaphenoxyethylamine, gamma-phenoxypropylamine, beta-phenoxyalpha-methylethylamine, and betaphenoxypropylamine.

Other suitable amines are the kind described in British Patent No. 456,517 andtmay be illustrated by Another example of such droxyethylgalactamine, and N-hydroxyethylfructamine.

Other suitable amines may be illustrated by Y uocu oomon in ab em emon JHa CH: 1 on-grdrcnron I 5 =1 Y cmt lomou O OH:

See, also, corresponding hydroxylated amines which be obtained from rosin or similar raw materials and def scribed in U. S. Patent No. 2,510,063, dated June 6, 1950, to Bried. Still other examples are illustrated by treatment of certain secondary amines, such as the following, witha mole of an oxyalkylating agent as described; phenoxyethylamine, phenoxypropylamine, phenoxyalphamethylethylamine, and phenoxypropylamine.

Polyamines free from a hydroxyl group may be illustrated by the following:

CH; CH: HczHtNCgHlN H C H 3 H NpropyleneNpropyleneN\ The fourth category consists of polyamines having hydroxylated groups which may be characterized by the following: 7

CH3\ CH! NCaHlOCzH4N HOCzHi 02114011 CaHs HOCzHi Z-undecylimidazoline 2-heptadecylimidazoline. 2-oleylimidazoline I 1-N-decylaminoethyl,2-ethylimidazoline Z-methyLl hexadecylaminoethylaminoethylimidazolinel-dodecylaminopropylimidazoline l-(stearoyloxyethyl) aminoethylimidazoline 1-stearamidoethylaminoethylimidazoline 1- (N-dodecyl) -acetamidoethylaminoethylimidazoline- 2-heptadecyl,4,5-dimethylirnidazoline 1-dodecylaminohexylimidazoline r 1-stearoyloxyethylaminohexylimidazoline Z-heptadecyl,l-methylaminoethyl tetrahydropyrimidine 4-methy1,2-dodecyl,1-methylaminoethylaminoethyl tetrahydropyrimidine A compound having no basic secondary amino radical but a basic primary amino radical can be reacted with a mole of an alkylene oxide, such as ethylene oxide, propylene oxide, glycide, etc., to yield a perfectly satisfactory reactant for the herein described condensation procedure. This can be illustrated in the following manner by a compound such as 2-heptadecyl,l-aminoethylimidazollne which can be reacted with a single mole of ethylene oxide, for example, to produce the hydroxy ethyl derivative of Z-heptadecyl,l-aminoethylimidazoline, which can be illustrated by the following formula:

Other reactants may be employed in connection with an initial reactant of the kind described above, to wit, Z-heptadecyl,l-aminoethylimidazoline; for instance, reaction with an alkylene imine such as ethylene imine, propylene imine, etc. If reacted with ethylene imine the net result is to convert a primary amino radical into a secondary amino radical and also introduces a new primary amine group. If ethylene imine is employed, the net result is simply to convert 2-heptadecyl,l-arninoethylimidazoline into 2 heptadecyl,l diethylenediamino imidazoline. However, if propylene imine is used the net result is a compound which can be considered as being derived hypothetically from a mixed p'olyalkylene amine i. e., one having both ethylene groups and a pro The products obtained by the herein described processes represent cogeneric mixtures which are the result- Sincethe resin,

of a condensation reaction or reactions. molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealizedsimplification, it is difiicult to actually depict the final product of the cogeneric mixture except in ,terms of the process itself.

The herein described amine-modified resins are ob-. tained from furfural and not formaldehyde. Due to the greater reactivity of furfural forreasons previously explained as far as I am aware one cannot substitutefurfural for formaldehyde in the manufacture of resins of the phenol-amine-aldehyde type. Generally speaking, the

for example, U. S. Patent No. 2,031,557 to Bruson. Since the condensation products. obtained are not heat-convertible andsince temperature up to 150 C. or thereabouts may be employed, it is obvious that the procedure becomescomparatively simple. Indeed, perhaps no description isnecessary over and above what has been said previously, in light of subsequent examples. However, for purpose of clarity the following details are included.

A convenient piece of equipment for preparation of these cogeneric mixtures is a resin pot of the kind described in aforementioned U. S. Patent No. 2,499,368. In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction if employed as subsequently described; in fact, usually it is apt to be a solid at distinctly higher temperatures, fer instance, ordinary room temperature. Thus, we have found it convenient to use a solvent and particularly one which can be removed readily at a comparatively moderate temperature, for instance, at 150 C. A suitable solvent is usually-benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such or similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can use an oxygenated solvent such as'a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively non-volatile solvent such as dioxane or the diethylether of ethyleneglycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necessary to use an initial resin which is soluble only in an oxygenated solvent as notedgand it is not necessary to have a single phase system for reaction.

In many instances furfural itself has a solvent effect and thus presents less difiiculty from the standpoint of reaction containing a formaldehyde which not only is a poor solvent but also usually is used in aqueous form. Furfural, of course, is substantially anhydrous. Of course, water is formed in the condensation reaction. If the solvent is completely removed at the end of the process, no problem is involved if the material is used for any subsequent reaction. However, if the reaction mass is going to be subjected to some further reaction where the solvent may be objectionable as in the case of ethylyor hexyl alcohol, and if there is to be subsequent oxyalkylation, then, obviously, the alcohols should not be used or else it should be removed. The fact that an oxygenated solvent need not be employed, of course, is an advantage for reasons stated.

Another factor, as faras the selection of solvent goes,

is whether or not the cogeneric mixture obtained at the end of the reaction is to be used as such or in the salt form. The cogeneric mixtures obtained are apt to be solids or thick viscous liquids in which there is some change from the initial resin itself, particularly if some of the initial solvent is apt to remain without complete removal. Even if one starts with a resin which is almost water-white in color, the products obtained are almost invariably a black or black-red in color. Indeed, the mere use of furfural itself seems to produce at least a type of material that gives the product a darker color and, indeed, considerably darker than comparable products derived from formaldehyde.

By and large, the melting point is apt to be lower and the products may be more sticky and more tacky than the original resin itself. Depending on the resin selected and on the amine selected the condensation product or reaction mass on a solvent-free basis may be hard, resinous and comparable to the resin itself.

The products obtained, depending on the reactants selected, may be water-insoluble, or watcr-dispersible, or water-soluble, or close to beingwater-soluble. Water solubility is enhanced, of course, by making a solution in the acidified vehicle such as .a dilute solution, for instance, a 5% solution of hydrochloric acid, acetic acid, hydroxyacetic acid, etc. One also may convert the finished product into salts by simply adding a stoichiometric amount 1dr selected acid and removing any water In fact,

present by refluxin with benzene er the like. the selection of the solvent employed may depend in part whether or not the product at the completion of the reaction is to be converted into a salt form.

In the next succeeding paragraph it is pointed out that frequently it is convenient to eliminate all solvent, using a temperature of not over C. and employing vacuum if required. This applies, of course, only to those circumstances where it is desirable or necessary to remove the solvent. Petroleum solvents, aromatic solvents, etc., can be used. The selection of solvent, such as benzene, xylene, or the like, depends primarily on cost, i. e., the use of the most economical solvent and also on three other factors, two of which have been mentioned previously; (a) is the solvent to remain inthe reaction mass without removal? (b) is the reaction mass to be subjected to further reaction in whichthe solvent, for instance, an alcohol, either low boiling or high boiling, might interfere as in the case of oxyalkylation? and the third factor isthis (c) is an effort to be made to purify the. reaction mass by the usual procedure as, for example, a water-wash to remove any unreacted low molal soluble amine, if employed and present after reaction? Such procedures are well known and, needless to say, certain solvents are more suitable than others. Everything else being equal, we have found xylene the most satisfactory solvent.

I have found no advantage in using a low temperature, approximately room temperature, at'the start of the reaction although this is sometimes done purely as a matter of convenience. Indeed, using furfural I have usually done nothing more than prepare the reaction mixture, add a suitable amount of xylene, and reflux for approximately 3 to 6 /2 hours at temperatures varying, as the case may be, from 135 to C. Where the amine has a comparatively low basicity I have sometimes added a small amount or approximately 1% of sodium methylate.

However, using a xylene-benzene mixture, for instance, approximately parts of benzene and 35 parts of xyene, and a phase-separating trap to eliminate water, I have found that I could employ temperatures between 90 and 100 C., and eliminate the water of condensation by refluxing at this temperature. However, I have found no particular advantage in using this low temperature over and above the high temperature previously noted.

Example 1b The resin employed was the one previously designated as 28a and had a molecular weight of approximately 600. grams of this resin were dissolved in an equal weight of xylene and 61 grams of di-isopropanolamine added. 58 grams of furfural were added and the mixture stirred for about 30 minutes and then the temperature allowed to rise to 140 C., where it was allowed to reflux for 6 hours. During this refluxing period a phase-separating trap was used to remove the water of formation. 1 At the end of this time the reaction was complete and the product was obtained in the form of a xylene solution. A small sample was evaporated to eliminate the xylene. The resultant product was a highly viscous, tacky inaterial, being black incolor with a reddish tinge.

14 acids which may be low molal or high molal, and polycarboxy acids of the kind previously enumerated.

TABLE II Solvent Max. Resin v Fur- (xylene untemp. Ex. N amt, Secondary amine Amt, fural, less other- 'Ilme pe during grams grams amt. wise noted), n'o'd, hrs. reaction,

- grams C.

175 Di-isopropylamine 61 58 175 6 140 150 Di-n-butylamine.. 65 48 150 4 150 150 Di-ethylamine. 37 48 150 4 140 150 Di-cyclohexylamim- 91 48 150 6 160 300 or honneh. 87 96 300 5. 150 300 Di-2-ethylhexylamine 241 96 300 3. 5 160 225 Bis-(1,3-dimethylbutyl)amine. 139 72 225 225 Di-isopropanolamine 100 72 225 2 150 225 a-Methylbenzylethanolamine- 124 72 225 2. 5 155 225 Di-ethanolamine 79 72 225 1. 75 150 225 Aminoethyl ethanolamine. 78 72 225 1. 5 130 225 Diethanolamine 79 72 "55-170 2 93 225 0 79 72 *55170 2 95 p 225 do 131. 5 128 55-170 2 9 225 Diisopropanolamine 174 128 225 1. 33 125 236 Di-isopropylamine 61 58 236 6 140 197 D1-n-buty1amine. 65 48 197 4 150 197 Di-ethylamine 37 48 197 4 140 197 Di-cyclohexylannne 91 48 197 6 Y 160 393 Morpholine 87 96 393 5. 5 150 393 Di(2ethylhexyl)amme 241 96 393 3. 5 160 197 N-methyl 54 48 197 3 160 295 Di-(beta-phenylethyDamine- 169 72 295 3. 5 155 295 Di-isopropanolamine 100 72 295 2 150 225 Di-ethanolamine 79 72 295 1. 75 150 188 Di-isopropylamine 61 58 225 6 140 188 Di-n-butylamiue 65 48 188 4 150 188 Di-ethylamine- 37 48 188 i 4 140 374 Di-cyclohexyla 91 48 188 6 160 374 M0rph0line 87 96 374 5. 5 150 188 Di-(Z-ethylhexy 241 96 374 3. 5 160 280 N-methylaniline 54 48 188 3 160 280 Di-(beta-phenylethyDa 169 72 280 3. 5 155 280 Di-isopropanolamine 100 72 280 2 150 280 Di-ethanolaimne... 79 r 72 280 1.75 150 N OTE .In the above examples no catalyst was added. In some duplications of the above small amounts-of catalyst were added up to 1% to 2% of either powdered caustic soda or powdered sodium methylate. No advantage Was noted in the use of a catalyst provided the amine was sufiiciently basic.

In Examples 12b, 13b and 14!) indicated by the double asterisk the solvent was a mixture of 170 parts of benzene and 55parts of xylene.

The mole] ratio of resin to amine to aldehyde was 1 to 2 to 2, except in Examples 140 and 15b Where the ratio was 1 to 3.5 to 3.5 in both instances.

In Examples through b the resin employed was the one identified as Example 28a.

In Examples 16!) through the resin employed was the one identified as Example 32a, and in Examples 26!) through 3517 the resin employed was identified as Example 39a.

PART 4 As to the use of conventional demuls'ifying agents reference is made to U. S. Patent No. 2,626,929, dated Janua'ry 7, 1 953, to De Groote, and particularly. to Part3.

Everything thatappears therein applies with equal force and efiect to the instant process, noting-only that where reference is made to Example 13b in said text beginning in column 15 and ending in column 18, reference should be .to Example 8b, herein described.

PART 5 The products described in Part 4 have utility in at least two distinct waysthe products as such, or in the form of some simple derivative, such as the salt which can be used in numerous arts subsequently described. Also, the products can serve as initial materials for more complicated reactions of the kind previously mentioned, -to wit,

theymay be subjected to oxyalkylation, particularly oxyethylation, or oxypropylation or oxybutylation to give products which are not only valuableifor the purpose described in regard to the parent material or. the salts of'the parent material, but also for other purposes; Likewise, since the tertiary amino nitrogen atom is present the products can readily be reacted with suitable reactants such as chloroacetic acid esters, benzylchloride,

alkyl halides, esters of sulfonic acids, methyl sulfate, or

The products herein described as such and prepared in accordance with this invention can be used as emulsi' fying agents, for oils, fats and waxes, as ingredients in insecticides compositions, or as detergents and wetting agents in thelaundering, scouring, dyeing, tanning and mordanting industries. .They also may be used for preparing boring or metal-cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes. a

Other uses include the preparation or resolution of petroleum emulsions, whether of'the Water-in-oil type or oil-in-water type. They may be used as additives in connection with other emulsifying agents; they may be employed to contribute hydrotropic eflfects; they may be used as anti-strippers in connection with asphalts. They maybe used to prevent corrosion, particularly the corrosionof ferrous metals for various purposes and particularly in connection with the production of oil and gas, and also in refineries where crude oil is converted into various commercial products. The products may be used industrially to inhibit or stop microorganic growth or other objectionable lower forms of life, such as the growth of algae, or the like; they may be used to inhibit the growthof bacteria, molds, etc.; they are valuable additives to lubricating oils, both those derived from petroleum and synthetic lubricating oils, and also to hydraulic brake fluids of the aqueous or nonaqueous type. Some have definite anti-corrosive action. They may be used in connection with. other processes where they are injected intoan oil or gas well for the purpose of removing a mud sheath, increasing the ultimate flow of fluid from the surrounding strata, and particularly in the secondary recovery operations using aqueous flood waters. They may be used also in dry cleaners soaps.

cyclohexylamine.

- particularly a sulfonic any sulfonic acid. s s

"I have found the products herein described are of i unusual utility for preventing the I in fuel oil during storage. I I

' Having'thus' described my invention,- what I claim as With regard to'the above statements, reference is made particularly to thetuse ofthe materials assuchyonin I the form of a salt; the salt form refers to a salt involving either one or both basic'nitrogen-atoms- ;bviously,the I saltform involves a modification in which the hydrophile i character can either be increased or decreasedand, in-

versely, the hydrophobe character can bedecreased or increased. For example, neutralizing the product. with practically anylow molal acid, such as acetiCTacidQIiy droxy. acetic acid, lactic acid, or nitric acid, is apt to markedly'increasethe hydrophile effect. I One may alsouse acids of the type,

more than 32carbon'atoms. .They are obtained from I higher fatty acids and include alsoresin acidssuch as 'abietic acid, and petroleum acids: such as naphthenie I acids and acids obtained by the oxidation of wax; One

I Y can also. obtain new products having unique properties by combination with poly-basic acids, such, as diglycolic acid, oxalic acid, dimerized acids from linseed oil, etc. The most common examples, of eourse,.are the higher fatty acids having generally to :18 carbon atoms. I I

have found, that a particularly valuable anti-corrosive v 7 agent can be obtained from. any suitable resin and foimal- I dehyde provided the secondary: amine isvhydroxyethyl The corrosion inhibitingproper-ties of this compound can be increased'by neutralization: with either one ortwo moles of anon-soluble sulfonic: acid,

acid of the type known as mahog new and desire to secure by Letters Patent is:

1-. The process of breaking petroleum emulsi'ons of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products; said synthetic hydrophile products being the reaction products obtainedby condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenolaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard tomethylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula in which 'R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic secondary amine free, from any primary amino radical and having not "2. The process. ofclaim :lwith the proviso that there be an alkanol radicalattached to at least one amino nitrogen atom. r

3. The process of breaking petroleum emulsions of the water-imoiltype, characterized by subjecting the ,Qemulsionr to the action-of a demulsifier including ,syn-

.thetic hydrophile products; said synthetichydrophile products being the reaction products obtainedby condensing I (a) an oxyalkylatidmsusceptible; fusible, non-oxygenated I organic solvent-soluble, water-insoluble;low-stage phenols aldehyde resin having anaverage'molecular weight, cor- I responding to at least 3 and not. over 6 phenolic nuclei per resin moleculersaid resin being difunctional only in regard tomethyloI- fo'rming reactivity; said resin being derived by reaction between a difunctional monohydricy phenol and an ald'ehydehaving not over 8 carbon atoms and reactive toward said phenol; said resin being formed; I V in the substantial absence of. phenols of functionality greater than 2; said phenol being of the formula in which is an; aliphatic-hydrocarbon radical having I I :at least 4 and not more-than 24 carbon atoms and separation of sludge i i I the water-in-oil type characterizedby subjecting the emulsubstituted in the'2,4,6 position; blca vbasic 'hydroxylated I secondarymonoamine having notflmore than 32 carbon I atoms in any group attachedto the amino nitrogen atoms being the reaction products obtained'by condensing (a) an oxyalkylanon-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low stage phenolaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in' regard to methylol-forming reactivity; said resin being derived by reaction between a difunc'tional monohydric phenol and an aldehyde having, not over 8, carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenolwbeing of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having'not morethan 32 carbon atoms in any group attached to the amino nitrogen atom and reactive towards furfural; and (c) furfiurah'said condensation reaction being conducted at a'temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and-resultants of reaction; with the added proviso. that the condensation reaction be conducted so as to produce Lasignificant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule;"a'rid with the further proviso that the resinousucondensation product resulting from the process be heat-stable.

S. The process of breaking petroleum emulsions of sion to the action of a demulsifier including synthetic "17 hydrophile products; said synthetic hydrophile products being the reaction products obtained by condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenolaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between, a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactivetoward said phenol; said resin being formed in the substantial absence of phenol of functionality greater than 2; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom and reactive towards furfural; and (c) furfural; said condensation reaction being conductedat a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three'reactants have contributed part of the ultimate molecule by virtue of a furfural-derived substituted methylene bridge connecting the amino nitrogen atom'witha resin molecule; with the further proviso that the ratio of reactants be approximately 1,2 and 2 respectively; and with the final proviso that the resinous condensation product resulting from the process be heat-stable. I

'6. The process of breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products; said synthetic hydrophile products being the reaction products obtained by condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenolaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional only in regard to methylol-forming reaction; said resin being derivedtby reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol;

resin being formed in the substantial absence of phenols" of functionality greater than 2; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom and reactive towards furfural; and (c) furfural said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a v the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1,2 and 2, respectively, with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable.

7 The process of breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products; said synthetic hydrophile products being the reaction products obtained by condensing (a) an oxyethylation-susceptible, fusible, nonoxygenated organic solvent-soluble, water-insoluble, low-' stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of phenols of functionality greater than'2; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6, position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom and reactive towards furfural; and (c) furfural said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a furfural-derived substituted methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1,2 and 2,;respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable.

8. The process of breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products; said synthetic hydrophile products bemg the reaction products obtained by condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenolformaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom and reactive towards turfural; and (c) furfural said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a furfural-derived substituted methylene bridge connecting the amino nitro gen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1,2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the the reaction products obtained by condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenolformaldehyde resin having an average molecular Weight corresponding to at least 3 and not over 5 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a'difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6, position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amine nitrogen atom and reactive towards furfural; and (c) furfural said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a furfural-derived substituted methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1,2 and 2, respectively; with the further proviso 20 that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable.

10. The process of breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products; said synthetic hydrophile products being the reacting products obtained by condensing (a) an oxyethylation-susceptible, fusible, nonoxygenated organic solvent-soluble, water-insoluble, lowstage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 5 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula 1 in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2, 4, 6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom and reactive towards furfural; and (c) furfural said condensation reaction being conducted at a temperature above the boiling point of water and below C., with the proviso that the condensationreaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a furfural-derived substituted methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensationproduct resulting from the process be heat-stable.

References Gited in the file of this patent UNITED STATES PATENTS 

1. THE PROCESS OF BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING SYNTHETIC HYDROPHILE PRODUCTS; SAID SYNTHETIC HYDROPHILE PRODUCTS BEING THE REACTION PRODUCTS OBTAINED BY CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOLALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEIPER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF PHENOLS OF FUNCTIONALITY GREATER THAN 2; SAID PHENOL BEING OF THE FORMULA 